Cu-Ni-Sn: A Key System for Lead-Free Soldering

Being the most complex constituent of the quaternary system Ag-Cu-Ni-Sn, the ternary system Cu-Ni-Sn is the key system for the investigation of the interactions of Ag-Cu-Sn solder alloys with Ni as a contact material. Although this system has been thoroughly studied in the literature, there are still many uncertainties left. In the present work, a study of the phase equilibria in four isothermal sections at 220, 400, 500, and 700°C of the Cu-Ni-Sn system was carried out following a comprehensive literature study. The methods employed were x-ray diffraction (XRD), metallography, and scanning electron microscopy including electron probe microanalysis. The ternary solubilities of the Ni₃Sn₂-Cu₆Sn₅ and Ni₃Sn-Cu₃Sn fields were characterized in detail. So far no continuous solubility between the respective phases has been found. At 25 at.% Sn the existence of two ternary compounds formed from the BiF₃-type (Cu,Ni)₃Sn phase and reported in literature could be confirmed. On the other hand, our results differ significantly from the very recent literature related to lead-free soldering.     

Microstructure, solderability, and growth of intermetallic compounds of Sn-Ag-Cu-RE lead-free solder alloys

The near-eutectic Sn-3.5 wt.% Ag-0.7 wt.% Cu (Sn-3.5Ag-0.7Cu) alloy was doped with rare earth (RE) elements of primarily Ce and La of 0.05–0.25 wt.% to form Sn-3.5Ag-0.7Cu-xRE solder alloys. The aim of this research was to investigate the effect of the addition of RE elements on the microstructure and solderability of this alloy. Sn-3.5Ag-0.7Cu-xRE solders were soldered on copper coupons. The thickness of the intermetallic layer (IML) formed between the solder and Cu substrate just after soldering, as well as after thermal aging at 170°C up to 1000 h, was investigated. It was found that, due to the addition of the RE elements, the size of the Sn grains was reduced. In particular, the addition of 0.1wt.%RE to the Sn-3.5Ag-0.7Cu solder improved the wetting behavior. Besides, the IML growth during thermal aging was inhibited.     

The effect of Ag content on the formation of Ag3Sn plates in Sn-Ag-Cu lead-free solder

The formation of Ag₃Sn plates in the Sn-Ag-Cu lead-free solder joints for two different Ag content solder balls was investigated in wafer level chip scale packages (WLCSPs). After an appropriate surface mount technology reflow process on a printed circuit board, samples were subjected to 150°C high-temperature storage (HTS), 1,000 h aging, or 1,000 cycles thermal cycling test (TCT). Sequentially, the cross-sectional analysis was scrutinized using a scanning electron microscope/energy dispersive spectrometer (SEM/EDX) to observe the metallurgical evolution of the amount of the Ag₃Sn plates at the interface and the solder bulk itself. Pull and shear tests were also performed on samples. It was found that the interfacial intermetallic compound (IMC) thickness, the overall IMC area, and the numbers of Ag₃Sn plates increase with increasing HTS and TCT cycles. The amount of large Ag₃Sn plates found in the Sn-4.0Ag-0.5 Cu solder balls is much greater than that found in the Sn-2.6Ag-0.5Cu solder balls; however, no significant difference was found in the joint strength between two different Ag content solder joints.     

Effect of thermal cycling on the growth of intermetallic compounds at the Sn-Zn-Bi-In-P lead-free solder/Cu interface

The low-temperature Sn-9Zn-1.5Bi-0.5In-0.01P lead-free solder alloy is used to investigate the intermetallic compounds (IMCs) formed between solder and Cu substrates during thermal cycling. Metallographic observation, scanning electron microscopy, transmission electron microscopy, and electron diffraction analysis are used to study the IMCs. The γ-Cu₅Zn₈ IMC is found at the Sn-9Zn-1.5Bi-0.5In-0.01P/Cu interface. The IMC grows slowly during thermal cycling. The fatigue life of the Sn-9Zn-1.5Bi-0.5In-0.01P solder joint is longer than that of Pb-Sn eutectic solder joint because the IMC thickness of the latter is much greater than that of the former. Thermodynamic and diffusivity calculations can explain the formation of γ-Cu₅Zn₈ instead of Cu-Sn IMCs. The growth of IMC layer is caused by the diffusion of Cu and Zn elements. The diffusion coefficient of Zn in the Cu₅Zn₈ layer is determined to be 1.10×10⁻¹² cm²/sec. A Zn-rich layer is found at the interface, which can prevent the formation of the more brittle Cu-Sn IMCs, slow down the growth of the IMC layer, and consequently enhance the fatigue life of the solder joint.     

Reliability of adhesion strength of the Sn-9Zn-1.5Ag-0.5Bi/Cu during isothermal aging

The reliability of adhesion strength of the Sn-9Zn-1.5Ag-0.5Bi/Cu during isothermal aging has been investigated. Due to the growth and decomposition of the intermetallic compound (IMC), the adhesion strength varies with aging at 150°C from 100, 400, and 700–1,000 h as wetted at 250°C for 60 sec. The IMC layers are determined at the Sn-9Zn-1.5Ag-0.5Bi/Cu interface by an x-ray diffractometer (XRD), an optical microscope (OM), a scanning electron microscope (SEM), an energy-dispersive spectroscope (EDS), and a transmission electron microscope (TEM). The adhesion strength has been investigated by the pull-off test. The results show that the Cu₆Sn₅, Cu₅Zn₈, and Ag₃Sn IMCs are identified at the Sn-9Zn-1.5Ag-0.5Bi/Cu interface as aging. The adhesion strengths are 12.44±0.58, 8.57±0.43, 5.50±0.78, 4.32±0.78, and 3.32±0.43 MPa for aging times of 0 h, 100 h, 400 h, 700 h, and 1,000 h, respectively.     

Effect of reflow and thermal aging on the microstructure and microhardness of Sn-3.7Ag-xBi solder alloys

This work investigates the effect of reflow and the thermal aging process on the microstructural evolution and microhardness of five types of Sn-Ag based lead-free solder alloys: Sn-3.7Ag, Sn-3.7Ag-1Bi, Sn-3.7Ag-2Bi, Sn-3.7Ag-3Bi, and Sn-3.7Ag-4Bi. The microhardness and microstructure of the solders for different cooling rates after reflow at 250°C and different thermal aging durations at 150°C for air-cooled samples have been studied. The effect of Bi is discussed based on the experimental results. It was found that the microhardness increases with increasing Bi addition to Sn-3.7Ag solder regardless of reflow or thermal aging process. Scanning electron microscopy images show the formation of Ag₃Sn particles, Sn-rich phases, and precipitation of Bi-rich phases in different solders. The increase of microhardness with Bi addition is due to the solution strengthening and precipitation strengthening provided by Bi in the solder. The trend of decrease in microhardness with increasing duration of thermal aging was observed.     

Effects of strain rates and biaxial stress conditions on plastic yielding and flow stress of solder alloys

The rate-dependent mechanical properties of Sn3.8Ag0.7Cu (SAC387) Pb-free alloy and Sn-Pb eutectic alloy were investigated in this study under pure shearing and biaxial stress conditions with thin-walled specimens using a servo-controlled tension-torsion material testing system. The pure shearing tests were conducted at strain rates between 6.7 × 10⁻⁷ and 1.3 × 10⁻¹/sec. In addition, axial tensile stresses were superimposed onto the shearing samples to examine the effects of biaxial stress conditions on the yielding and on post-yielding plastic flow of the solder alloys. Strain hardening is observed for the Pb-free alloy at all the tested strain rates, while strain softening happens with the Sn-Pb eutectic solder at low strain rates. Special tests were also conducted for sudden strain-rates changes and stress relaxation for the purpose to develop a viscoplastic model to simulate time-dependent multiaxial deformation and to assess damage and fatigue life of general solder interconnections.     

On the advantages of using a hypoeutectic Sn-Zn as lead-free solder material

Hypoeutectic Sn-Zn may be a better choice than the eutectic Sn-9Zn as a lead-free solder. We checked the non-equilibrium melting behaviors of a series of Sn-Zn alloys (2.5-9 wt.% Zn) by differential thermal analysis, and found that at a heating rate of 5 °C/min, Sn-6.5Zn behaves the same way as the eutectic Sn-9Zn in melting. Dipping and spreading tests were carried out to characterize the wettability of Sn-Zn alloys on Cu. Both tests indicated that Sn-6.5Zn has significantly better wettability to Cu than Sn-9Zn does. The reaction layers formed during the spreading tests were examined. For all samples with 2.5-9 wt.% Zn, two reaction layers are formed at the interface, a thick and flat Cu₅Zn₈ layer adjacent to Cu and a thin and irregular Cu-Zn-Sn layer adjacent to the alloy. The total thickness of the reaction layers between the alloy and Cu was found to remarkably decrease with decrease of the Zn concentration.     

Effect of indium addition in Sn-rich solder on the dissolution of Cu metallization

An investigation has been carried out to study the dissolution of the Cu pad of the ball-grid-array (BGA) substrate into the molten Sn–9%In–3.5%Ag–0.5%Cu, Sn–3.5%Ag–0.5%Cu and Sn–0.7%Cu (wt.%) solder alloys. A fixed volume of BGA solder ball (760 μm dia) was used on a 13 μm thick Cu pad with a diameter of 650 μm. The dissolution measurement was carried out by measuring the change of Cu pad thickness as a function of time and temperature. Scanning electron microscopy was used to examine the microstructure of the solder joint and to measure the consumed thickness of Cu. The dissolution of Cu in Sn–3.5%Ag–0.5%Cu solder is higher than the other two lead-free solders. The presence of indium in the solder plays a major role in inhibiting the consumption of Cu in the soldering reaction. The intermetallic compounds (IMCs) formed at the Sn–9%In–3.5%Ag–0.5%Cu/Cu interface are determined as a scallop-shaped Cu₆(Sn, In)₅. Bulk of the Sn–9%In–3.5%Ag–0.5%Cu solder also contains Cu₆(Sn, In)₅ and Ag–In–Sn precipitates embedded in the Sn-rich matrix. It is also found that more Cu-containing Sn–0.7%Cu solder shows lower Cu consumption than Sn–3.5%Ag–0.5%Cu solder at the same heat treatment condition.     

Manoeuvring and vibration reduction of a flexible spacecraft integrating optimal sliding mode controller and distributed piezoelectric sensors/actuators

This investigation is to apply optimal sliding mode (OSM) control theory and distributed piezoelectric sensor/actuator technology to vibration control of a flexible spacecraft. An approximate analytical dynamic model of a slewing flexible spacecraft with surface‐bonded piezoelectric sensors/actuators is developed using Hamilton's principle with discretization by assumed model method. To satisfy pointing requirements and simultaneously suppress vibration, two separate control loops are adopted. The first uses the piezoceramics as sensors and actuators to actively suppress certain flexible modes by designing a positive position feedback (PPF) compensators that add damping to the flexible structures in certain critical modes in the inner feedback loop; then a second feedback loop is designed using OSM control to slew the spacecraft. The OSM controller minimizes the expected value of a quadratic objective function consisting of only the states with the constraints that the error states always remain on the intersection of sliding surfaces. The advantage in this method is that the vibration reduction and attitude control are achieved separately in the two separate feedback loops, allowing the pointing requirements and simultaneous vibrations suppression to be satisfied independently of one another. An additional attraction of the design method is that the selection of PPF gain is determined by introducing a cost function to be minimized by the feedback gains which are subject to the stability criterion at the same time, such that the feedback gains are selected in a more systematical way to avoid the arbitrary selecting of feedback gains. The proposed control strategy has been implemented on a flexible spacecraft, which is a hub with a cantilever flexible beam appendage and can undergo a single axis rotation. Both analytical and numerical results are presented to show the theoretical and practical merits of this approach. Copyright © 2006 John Wiley & Sons, Ltd.